Light sensitive papers and other bases and light sensitive layers therefore



Patented May It), 1932 i UNITED STAT S PATENT arm-El f BQBER'I LANTZ, OF 'SAINT-DENIS, FRANCE, ASSIGNOR To SOCIETE DESl ANGIEN'S ETABLISSEMENTS SALVATOBI, LEPEBCHE; FRANGIALLI & CIE, S'U'CCESSEURS, OF

EARLS, FRANCE, A CORPORATION OE FRANCE LIGHT SENSITIVE PAPERS AND OTHER BASES LIGHT SENSITIVE LAYERS & THEREFORE No Drawing. Application filed February 1, 1930, semi 110.4283, and 'inIrance February a, 192a.

This invention relates to the art-of making light sensitive layers and the production of I tive, the portions of the diazo-compound which are not protected by the dark portions of the picture will be destroyed and there remains a positive picture formed by the portions of the diazo-compound vthat have not been attacked. The picture may be visible or not, depending on whether the diazo-compound be. coloured or not-coloured. Theslightly coloured picture which is unstable when exposed to light may be transformed into a coloured and stable picture by treat ment with'a suitable compound, such as a phenol or an amine, under such conditions that the coupling reaction of the diazo-compound with the other component can take place. -This coupling reaction of the diazo compound may be produced, for example by treating the latent picture with an alkaline solution ofa phenol.

Attempts have been made to simplify the process by incorporating the coupling (.om-

' ponent with the di'azo-compound in thesausitive layer applied to'the paper or other suitable base. In such case, however, it is necessary to add an acid to the mixture constituting the sensitive layer in order to prevent premature coupling during. storage.- Proofs thus obtained can thus be developed by subjecting the sensitive layer to the action of an alkali, for example by treating the sensitive layer with an alkaline solutionor with an' atmosphere of gaseous ammonia.

In'a particular case, where'phloroglucine was used as thecoupling component,-it was found that premature coupling can be prevented by the addition to the mixt ureconstituting the sensitive layer, before exposure, of

hydroxylamine, which converts the phloroglucine into abody (triacetohexamethylenetrioxime) in which the coupling capacity is suspended, but can be restored by developing with an alkaline developer.

In accordance with my invention, layers sensitive to light, or papers or other suitable bases provided'with such layer, and which can be developed by the simple action of an alkaline developer, are produced by mixing with the diazo-compound in the sensitive layer,'no t a coupling component (phenol or aminefor example) itself, but a substance which will with the diazo-compound, few, if any, precau-.

tions are necessary to avoid premature coupling' The substance used to produce the coupling component for the diazo-compound should be stable in a neutral or slightly acid medium and be very rapidly transformed into the coupling component for the diazo-- compound, by the alkali used inthe developer. It will be seenthat my invention is based upon an entirely different principle, and is fully distinguished from the'two earlier pro'casses-above referred to. I

I have obtained excellent results by using naphthalene sultones as substances susceptlble to form coupling components for the diam-compounds. Sulto'nes do not combine with diaz'o-compounds and are stable in a nonalkaline medium. On the other hand, in the presence of an alkali, they are converted, by release of the sultone bond, .into compounds havingcoupling capacity. It is well known that these mula (with the possibility of substitution at 2, 3, 4,5, 6 or?) give naphthol sulfonaite-(l) in. the presence of an alkali, such as sodium-by, droxide, carbonate of sodium,etc.- and a naphproducts' having the general forthol sulphamide (2) in the presence of ammonia.

soul on The use of the above mentioned products- *enables photo raphic proofs to be made, which can be iept and stored without any coupling action in the presenceof very small quantities ofacid or without the addition of '1 any acid whatever even though the diazoused.

It is well known that sultones may be obtained by heatingthe diazo-compoundof a 1-8-naphthylaminc-sulphonic acid whether substituted or not. Under certain conditions therefore, it ma be advantageous to a ply a diazo compoun ,of this character to t e paper or other base and to convert it into a sultone by suitably heating said paper or other base before exposure. If the sensitive diazo-' compound used be stable at the temperature at which the diazo-compound of the 1-8- naphthylamine-sulphonic acid is converted into sultone, the heating may be carried out after both the 'diazo-com ounds have bee applied to the paper or oter base.

I shall now give'several examples to indicate the mode and manner of putting'my invention into execution, but it is to beunderstood that my invention is not to be consid:

ered as limited to the examples given, norany of them.

Ewample 1 3.1 parts of sulphate of thioaniline are diazotized in the usual manner in the presence of hydrochloric acid with a slight excess of sodium nitrite; after having removed the excess of nitrous acid with a solution of urea,

. a solution 'containin 6.2 parts of naphthalene-l-8-sultone- 4-su phonate of sodium (obtained ,by heating 1-naphthylamine-4-8-disulphonic acid) is added. The volume having been brought to 300 parts, the paper-or other suitable base is covered with the liquid and dried. After exposure to light and on developing with an a ueous solution of an alkali for example so ium carbonate, a red prooi will be obtained; development in an ammoniacal atmosphere gives amore bluish tint.

Eammple 2 1.6 parts of 4-aminodiphenylamine-2- sulphonic acid are diazotized in the usual tained with this solution are treated in the same manner as in the preceding example.

Development in an ammoniacal atmosphere gives a vlolet-blue plcture.

If a metallic salt be added the proofs aremore resistant to washing with water ,and

their shade changes; sulphate of nickelf'for example, produces a marked chan e in the shade which becomes highly reddis Example 3 parts of diphenylamine-4-diazonium sulphate .are dissolved in waterand to this I is added a solution of the diazo-compound,

obtained by diazotizing 0.5 parts ofl-aminonaphthalene-4-8-disulphonic acid in the presence of hydrochloric acid, and also 1,5 parts of citric acid. The total volume is brought to 50 arts.

TlhEphotographicpaper obtained with this solution is dried in an oven at.80 C. until a test proof obtained in the same manner, but without the addition of the diphenyldiazonium salt and placed in the oven at the same time with the other, shows no signs of coupling with an alkaline solution of .Betanaphthol.

Exposure. and-development is effected as in the previous examples. The proof developed in ammonia is violet black and that developed with a non-ammoniacal alkali is brownish-red.

Very similar results are obtained b substituting the diazo-con'ipound of l-nap thylamine-3-6-8-trisulphonic acid for the diazocon'pound of naphthylamine disulphonic ac1 Example 4 parts, the solutionis applied to the paper orother base.

. Development with gaseous ammonia gives a reddish violet proof. I An analogous paper can be obtained by substituting for the naphthosultone-sulphonic-1-8-4 acid its isomeric-acid 1-8-3,

Example 5 A sensitive paper or other base obtained with a weak (100 cc.) hydrochloric acid solution of the diazo-compound of thioaniline alone (obtained from 1.6 grams of sulphate of thio'aniline) is develo ed with an alkaline solution of Schaeifer sa t (sodium salt of 2- naphthol-6-sulphonic acid) the proofobtained is red,

E'abdmple 6 The same mode of operation as in Example 4 is followed, but the sultone is replaced by 2.3 parts of naphthol-G-sulphonate of'sodium and 9 parts of oxalic acid are added. Upon developing in sodium carbonate or with layers.

gaseous ammonia a bright red proof is obtained. p So far as I am aware, I am the first to discover that diazo-co'mpounds obtained by diazotizing thioaniline, aminon'aphtholdisulphonic RR acid and 4-aminodiphenylamine-2-sulphonic acid can be used as light sensitive diazo-components in light sensitive It is to be understood that the foregoing description is to be considered in all respects as illustrative and not restrictive, reference being had to the appended claims rather than to said description to indicate the scope ofthe invention.

I claim: I

1. Process for making light sensitive layers or a paper or other suitable base provided with such layer, which comprises mixing with a suitable light sensitive diazocompound, a naphthalene sultone adapted to form-a coupling component for said diazocollinpound when subjected -to the action of an al ali.

' 2. Process for making light sensitive layers or a paper or othersuitable base provided with such layer, which comprises removing the excess of nitrous acid from about 3.1 parts of sulphate of thioanili'ue diazotized in the presence of hydrochloric acid with a slight excess of sodium nitrite, and adding a soluof a diazo-compound obtained from about,

3.2 parts of aminonaphtholdisulphonic RR acid, a. solution of about 3.2 parts of the sodium salt of naphthosultone-sulphonic 1-8-4 acid. Y

5; A light'sensitive layer, or apaper or other suitable base provided with such layer, which comprises a mixture of a light sen- -action of an al 'sitive di'azo-compound and a naphthalene s ultone to form a'coupling component for said diam-compoundwhen subjected to the ali. 6. A light sensitive layer or a paper or 2 other suitable base provided with such layer,

which comprises a mixture of about-6.2 parts of naphthalene-1-8-sultone-4-sulphonate of sodium and about 3.1 partsof sulphate of thioaniline which has been diazotized in the presence of h drochloric acid with a sh ht excess of so ium nitrite and from WhlCh" the excess of nitrous acid has been removed.

7. A light sensitive layer or a paper or other suitable base provided with such layer, which comprises amixture of about 1.9 parts of 'naphthalene-1-8-sultone-3 sulphonic acid with about 1.6 parts of 4-aminodiphenylamine-2-sulphonic acid diazotized in the presence of hydrochloric acid.

8. A light sensitive layer or a paper orother suitable base provided with such layer, which comprises about 3.2 parts of a sodium salt of naphtho-sultone-l-8-4-sulphonic acid with about 3.2 parts of aminonaphtholdisulphonic RR acid applied in a weak hydrochloric acid solution.-

9. Process for making light sensitive laycr's. or a paper or other. suitable base provided with such layer, which'comprises mixing with a weak hydrochloric acid solution of a diazo-compound obtained from about 3.2 parts of aminonaphtholdisulphonic RR acid, a solution of about 3.2 parts of thesodium salt of naphthosultone-sulphonic 1-8-3 acid.

10. A light sensitive layer or apaper or other suitable base provided with such layer, which comprises about 3.2 parts of a sodium salt of naphtho-sultone-sul honic-1- 8-3 -.acid with about 3.2 parts 0 aminonaphtholdisulphonic. RR acid applied in a weak hydrochloric acid solution.

In testimony whereof, I have signed my name to this specification.

a ROBERT LANTZ. 

